Poly-oxycarbosilane compositions for use in imprint lithography

ABSTRACT

The present invention relates to compositions comprising poly-oxycarbosilane and methods for using the compositions in step and flash imprint lithography. The imprinting compositions comprise a poly-oxycarbosilane polymer, a silanol, a reaction initiator and optionally a pore generator.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.11/495,038, filed on Aug. 28, 2006, which is incorporated by referenceherein in its entirety.

FIELD OF THE INVENTION

This invention relates to compositions comprising poly-oxycarbosilaneand methods for using the compositions in step and flash imprintlithography.

BACKGROUND OF THE INVENTION

Semiconductor devices such as microprocessors, microcontrollers andcommunication chips are used extensively in electronic devices includingcomputers. Generally semiconductor devices include a plurality ofintegrated circuits (ICs). ICs can contain millions of transistors andother circuit elements fabricated on a single semiconductor chip.Semiconductor devices require many layers of wiring to interconnectdevices such as field effect and bipolar transistors into integratedcircuits. Two major factors limit the signal speed of advancedsemiconductor devices. The first is the wiring density which isgenerally a function of wire dimensions. The second is the capacitanceof the device which is a function of the dielectric constant of thematerial insulating the wires. Therefore, to increase signal speed forsemiconductor devices, there is an ongoing need for compositions andprocesses for fabricating semiconductor devices that have dense wiringand have low capacitance.

SUMMARY OF THE INVENTION

The present invention relates to compositions and methods for imprintlithography. A first aspect of the present invention relates to acomposition for use in manufacturing semiconductor devices. Thecomposition comprises a poly-oxycarbosilane polymer, a silanol and areaction initiator to promote crosslinking between thepoly-oxycarbosilane and the silanol. In a preferred embodiment, thereaction initiator is selected from a photoacid generator and a thermalacid generator. Optionally, the composition can also comprise a poregenerator.

A second aspect of the present invention relates to a method for forminga semiconductor structure. The method generally comprises (a) disposingon a substrate a precursor dielectric layer comprising a polymerizablecomposition comprising a silanol, a reaction initiator and apoly-oxycarbosilane; (b) pressing a relief pattern on a surface of atemplate into the exposed surface of the precursor dielectric layer; (c)polymerizing the precursor dielectric layer; (d) curing the precursordielectric layer to form a dielectric layer having thick and thinregions corresponding to the relief pattern; and lastly (e) depositing aconductive material onto the exposed surface of the dielectric layerafter the template has been removed. Suitably, the precursor dielectriclayer is a liquid. The dielectric material can be cured afterpolymerizing the precursor dielectric layer and before or after removingthe template.

BRIEF DESCRIPTION OF DRAWINGS

The features of the invention are set forth in the appended claims. Theinvention itself, however, will be best understood by reference to thefollowing detailed description of illustrative embodiments when read inconjunction with the accompanying drawings, wherein:

FIGS. 1A through 1F are cross sectional views of a method of fabricatinga dual damascene wire according to an embodiment of the presentinvention;

FIG. 2A a top view illustrating the section through which FIG. 1F istaken;

FIG. 2B is an isometric drawing of a trench and via opening asillustrated in FIG. 1F;

FIGS. 3A through 3C are cross sectional views of a method of fabricatinga dual damascene wire according to an embodiment of the presentinvention;

FIGS. 4A through 4C are cross sectional views of a method of fabricatinga dual damascene wire according to an embodiment of the presentinvention; and

FIG. 5 is an SEM photomicrograph of imprinted structures formed fromimprinting compositions according to an embodiment of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

The imprintable precursor dielectric compositions of the presentinvention include a polymerizable poly-oxycarbosilane polymer, a silanoland a reaction initiator. The precursor dielectric compositions mayfurther include a pore generator and/or a solvent. The compositions mayalso include other materials to improve the methods and compositions ofthe present invention such as beta-diketones, colloidal silica,colloidal alumina, surfactants, water, silane coupling agent, radicalgenerating agents, triazene compounds and the like.

The poly-oxycarbosilane polymer of the present invention is apolymerizable polymer comprising a repeating unit having a structureselected from one of the following structures I and II:

where R, R₁, R₂, and R₃ are independently selected from hydrido, C₁₋₆alkyl and haloalkyl, such as methyl, fluoroethyl, propyl; C₄₋₇cycloalkyl and halocycloalkyl; C₁₋₆ alkylenyl and haloalkylenyl; andC₆₋₁₂ aryl and haloaryl (where aryl includes alkylaryl), such as phenyl,naphthyl, methylphenyl and chlorophenyl; x is 1 to 4 preferably 1 to 2and n=2 to 5000, suitably 5 to 500.

In an alternative embodiment, one or more of R, R₁, R₂, and R₃ areindependently selected from a polymerizable substituent derived fromacrylate, methacrylate and vinyl ether such as C₃₋₄ alkylenylcarbonyloxyor C₅₋₁₀ cycloalkylenylcarbonyloxy. The polymerizable substituent couldpolymerizes in the process to form a carbosilane network. Alternatively,one or more of R, R₁, R₂, and R₃ could be independently selected from acarbosilane substituent known to those skilled in the art which wouldform a hyperbranched polymer in the process.

Suitable silanols include organosilicates, such as those disclosed inU.S. Pat. No. 5,895,263 to Carter et al. (incorporated herein byreference), including the family of organosilicates known assilsesquioxanes, (RSiO_(1.5))n. Suitable silsesquioxanes for the presentinvention include hydrido (R=hydrido), alkyl (R=methyl, ethyl, propyl,and higher alkyl), aryl (R=phenyl) or alkyl/aryl, vinyl, and copolymersthereof, as well as polymethylsilsesquioxane (PMSSQ), which arecommercially available from Owens Corning, JSR Micro and Shin-Etsu, forexample. Most commonly, the silsesquioxane is poly (methylsilsesquioxane), ((CH₃)SiO_(1.5))n, and n is 10 to 500 or more(including copolymers). As used herein organosilicates includesilsesquioxane thermoset resins generally represented by the formula(RSiO_(1.5))_(n) as described above, including copolymers of one or moreof the monomers (Si(R)_(1.5)), (SiO₂), (SiR₂O), and (R₃SiO), in which Ris defined above. The organosilicate suitably has a molecular weight ofabout 600 to 30,000 daltons.

Suitable silanols also include small silanol molecules such asR_(m)Si(OH)_(4-m) where each R_(m) is independently selected fromhydrido, C₁₋₆ alkyl and haloalkyl such as methyl, fluoroethyl andpropyl; C₁₋₆ alkenyl and haloalkenyl; C₆₋₁₂ aryl and haloaryl, such asphenyl, naphthyl, methylphenyl and chlorophenyl. The silanol can beadded to the composition as part of the mixture or as a coating onsilica nanoparticles.

Suitable reaction initators for the compositions of the presentinvention include photo and thermal radical initiators, photo-acid andthermal acid generators and photo and thermal base generators known tothose skilled in the art. Suitable photo radical initiators include butare not limited to: acetophenone, anisoin, anthraquinone,anthraquinone-2-sulfonic acid, (benzene)tricarbonylchromium, benzil,benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin methylether, benzophenone, 3,3′,4,4′-benzophenonetetracarboxylicdianhydride,4-benzoylbiphenyl, 2-benzyl-2-dimethylamino)-4′-morpholinobutyrophenone,4,4′-bis(diethylamino)benzophenone, 4,4′-bis(dimethylamino)benzophenone,camphorquinone, 2-chlorothioxanthen-9-one,(cumene)cyclopentadienyliron(II) hexafluorophosphate, dibenzosuberenone,2,2-diethoxyacetophenone, 4,4′-dihydroxybenzophenone,2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone,4,4′-dimethylbenzil, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone,diphenylbis(2,4,6-trimethylbenzoyl)phosphine oxide,4′-ethoxyacetophenone, 2-ethylanthraquinone, ferrocene,3′-hydroxyacetophenone, 4′-hydroxyacetophenone, 3-hydroxybenzophenone,4-hydroxybenzophenone, 1-hydroxycyclohexyl phenyl ketone,2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone,3-methylbenzophenone, methybenzoylformate,2-methyl-4′-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone,and 4′-phenoxyacetophenone, thioxanthen-9-one.

Suitable photo-acid generators include, but are not limited to:sulfonium salt, triphenylsulfonium perfluoromethanesulfonate(triphenylsulfonium triflate), triphenylsulfoniumperfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate,triphenylsulfonium perfluorooctanesulfonate, triphenylsulfoniumhexafluoroantimonate, triphenylsulfonium hexafluoroarsenate,triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide,triphenylsulfonium chloride, triphenylsulfonium iodide,2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate,2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate,tris(t-butylphenyl)sulfonium, diphenylethylsulfonium chloride,phenacyldimethylsulfonium chloride, halonium salts, diphenyliodoniumperfluoromethanesulfonate (diphenyliodonium triflate), diphenyliodoniumperfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate,diphenyliodonium, diphenyliodonium hexafluoroantimonate,diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodoniumtriflate, bis-(t-butylphenyl)-iodonium camphorsulfonate,α,α′-bis-sulfonyl diazomethanes, bis(p-toluenesulfonyl)diazomethane,methylsulfonyl p-toluenesulfonyldiazomethane,1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl) diazomethane,bis(cyclohexylsulfonyl)diazomethane, trifluoromethanesulfonate esters ofimides and hydroxyimides,(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide(MDT), nitrobenzyl sulfonate esters, 2-nitrobenzyl p-toluenesulfonate,2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzylp-trifluoromethylbenzenesulfonate, sulfonyloxynaphthalimides,N-camphorsulfonyloxynaphthalimide andN-pentafluorophenylsulfonyloxynaphthalimide, pyrogallol derivatives(e.g., trimesylate of pyrogallol), naphthoquinone-4-diazides, alkyldisulfones, s-triazine derivatives, sulfonic acid generators, tbutylphenyl-α-(p-toluenesulfonyloxy)-acetate,t-butyl-α-(p-toluenesulfonyloxy)acetate, N-hydroxy-naphthalimidedodecane sulfonate (DDSN), and benzoin tosylate and materialsrepresented by the following structures III, IV, and IV:

wherein T_(f)═CF₃S(O)₂O—.

Suitable thermal acid generators which generate acid upon thermaltreatment include, but are not limited to 2,4,4,6tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate andother alkyl esters of organic sulfonic acids. Compounds that generate asulfonic acid upon activation are generally suitable. Other suitablethermally activated acid generators are described in U.S. Pat. Nos.5,886,102 to Sinta et al. and 5,939,236 to Pavelchek et al.

The composition may optionally comprise a decomposable polymer, i.e., apore generator. The pore generator functions to reduce the dielectricconstant of the composition after thermal curing; however, the poregenerator also modulates the viscosity of the dielectric composition.Suitable pore generators include, but are not limited to: a linear orbranched polymer selected from the group consisting of polyesters,polylactides, polystyrenes, substituted polystyrenes, poly-alpha methylstyrenes, substituted poly-alpha methyl styrenes, aliphatic olefins,polynorbornenes, polyacrylates, polymethacrylates and aliphaticpolyethers. A suitable aliphatic polyether is selected from the groupconsisting of polyethylene oxide, polypropylene oxide andpolytetrahydrofuran. Cyclodextrins may also be used as a pore generator.

The pore generator polymers may be selected from hyperbranched polymers,a linear di- or triblock copolymer, a radial block copolymer or apolymeric unimolecular amphiphile. Optionally, the pore generator can bebonded as a substituent to the poly-oxycarbosilane.

Though not limited to any single use, the present invention may beadvantageously used to fabricate damascene and dual-damascene wires andvias.

The present invention combines step and flash imprint lithography withmaterials that can be converted to low dielectric constants (where k,the dielectric constant, is less than about 3.9) in order to fabricatedamascene and dual-damascene interconnect structures for integratedcircuits. Step and flash imprint lithography is used with aphotosensitive or thermally sensitive pre-dielectric material that ismolded between a template having a relief pattern and a substrate. Thematerial is exposed to actinic radiation or a thermal treatment and theresulting patterned dielectric layer, having a three dimensionalpattern, is used as part of a damascene or dual damascene process.

A damascene process is one in which wire trenches or via openings areformed in a dielectric layer, an electrical conductor of sufficientthickness to fill the trenches is deposited on a top surface of thedielectric, and a chemical-mechanical-polish (CMP) process is performedto remove excess conductor and make the surface of the conductorco-planar with the surface of the dielectric layer to form a damascenewires (or damascene vias). When only a trench and a wire (or a viaopening and a via) is formed the process is called single-damascene.

A dual-damascene process is one in which via openings are formed throughthe entire thickness of a dielectric layer followed by formation oftrenches part of the way through the dielectric layer in any givencross-sectional view. All via openings are intersected by integral wiretrenches above and by a wire trench below, but not all trenches needintersect a via opening. An electrical conductor of sufficient thicknessto fill the trenches and via opening is deposited on a top surface ofthe dielectric and a CMP process is performed to make the surface of theconductor in the trench co-planar with the surface the dielectric layerto form dual-damascene wires and dual-damascene wires having integraldual-damascene vias.

The present invention will be described in an exemplary dual damasceneprocess, for forming wires with integral wires and vias; however itshould be understood the method described is applicable to singledamascene processes for forming wires or vias.

FIGS. 1A through 1F are cross sectional views of a method of fabricatinga dual damascene wire common to both a first and a second embodiment ofthe present invention. In FIG. 1A, electrically conductive wires (orcontact studs) 105 are formed in substrate 100. A top surface of wires105 is coplanar with a top surface of substrate 100. An optional copperdiffusion barrier 110 is formed on the top surfaces of wires 105 andsubstrate 100. In one example, copper diffusion barrier 110 is siliconnitride.

In FIG. 1B, a pool of dielectric precursor material 115 is applied.Precursor dielectric material 115 is a liquid. Dielectric precursormaterial 115 includes a poly-oxycarbosilane polymer, a silanol and areaction initiator. The substituent groups of the poly-oxycarbosilanecrosslink with the silanol in the presence of reaction initiator. In oneexample, dielectric precursor material 115 can include about 5-50 wt %of a pore generator.

In FIG. 1C, an imprint template 120 includes a relief pattern made up ofplateaus 125 and 130 rising above a reference surface 135. Plateaus 130rise above plateaus 125. Imprint template 120 is pressed with a lowpressure (i.e., less than about 1 psi) toward substrate 100, and thepool of dielectric precursor material 115 (see FIG. 1C) is spread outover copper diffusion barrier 110, completely filling the spaces betweenplateaus 125 and 130 and reference surface 135 and a top surface ofcopper diffusion barrier 110.

In FIGS. 1D (FIG. 1D′ and FIG. 1D″), after exposure to actinic radiation(e.g., ultraviolet (UV) radiation) FIG. 1D′, or after a thermaltreatment (FIG. 1D″), the dielectric precursor material 115 (see FIG.1C) is converted (i.e. the poly-oxycarbosilane and the silanol arecross-linked) to a dielectric material 140.

In FIG. 1E, template 120 is then removed exposing a top surface 145 ofdielectric layer 140 and trenches 150 having integral pre-via openings155 formed in the dielectric layer. Trenches 155 are open to top surface145 of dielectric layer 140.

In FIG. 1F, a blanket etch is performed to remove any of dielectriclayer 140 remaining in the bottom of via openings 155 (see FIG. 1E) andan additional etch is performed to remove copper diffusion barrier 110at the bottom of the vias opening and expose wires 105. The blanket etchremoves a portion of top surface 145 (see FIG. 1E) and creates a new topsurface 145A of dielectric layer 140. Trench 150 (see FIGS. 1D) isdeepened to create trenches 150A and vias 155A. In one example, theblanket etch and the additional etch are reactive ion etches (RIEs).Alternatively, a single RIE etch may be performed to etch bothdielectric layer 140 and copper diffusion barrier 110.

FIG. 2A is a top view illustrating the section through which FIG. 1F istaken. In FIG. 2A, trenches 150A extend laterally and via openings 155Aare contained within the perimeter of trenches 150A. Alternatively, thetwo opposite sides of via openings 155A facing the sidewalls of thetrench may extend to those sidewalls.

FIG. 2B is an isometric drawing of a trench and via opening asillustrated in FIG. 1F. In FIG. 2B, via opening 150A is shown in cutawayand it is clear that trench 155A is not as deep as via opening 150A.

FIGS. 3A through 3C are cross sectional views of a method of fabricatinga dual damascene wire according to the first embodiment of the presentinvention. In FIG. 3A, dielectric layer 140 (see FIG. 1F) is heated to atemperature high enough to fully cure the dielectric layer creating aporous dielectric layer 160 having pores 162. The high temperature cureperforms two functions:

-   -   (1) the high temperature cure further improves the cross-linking        between the poly-oxycarbosilane and the silanol containing        materials forming a glass-like insulating film, and    -   (2) the high temperature decomposes and volatilize and drives        out carbonaceous materials such as pore generators,        non-cross-linked poly-oxycarbosilane, non cross-linked silanol,        photoacid generator and thermal acid generator.

The cure is preferably performed at a temperature of at least about 80°C. to about 600° C. for a period of about 5 to about 240 minutes. Thecured non-porous dielectric film (dielectric film without poregenerator) has a dielectric constant as low as 3.0. The cured porousdielectric film has a dielectric constant as low as 1.8.

In addition to or in place of the high temperature cures, a non thermalcure may be performed. Examples of non-thermal cures include but are notlimited to exposure to ultra-violet radiation, microwave radiation orelectron beams.

In FIG. 3B, a conformal electrically conductive layer 165 is formed onall exposed surfaces of porous dielectric layer 160 and wires 105 and anelectrically conductive layer 170 of sufficient thickness to overfilltrenches 150A (see FIG. 3A) is formed on top of conductive layer 165. Ina first embodiment, the conductive layer 165 comprises tantalum,tantalum nitride, titanium, titanium nitride or combinations thereof. Ina second embodiment, conductive layer 165 comprises a seed layer ofcopper formed, for example, by deposition or evaporation. In the firstembodiment, conductive layer 170 comprises tungsten. In the secondembodiment, conductive layer 170 comprises copper formed, for example,by electroplating.

In FIG. 3C, a chemical-mechanical-polish (CMP) is performed to formdamascene wires 175 having integral vias 180, the vias being in physicaland electrical contact with wires 105. Top surfaces 185 of wires 175 arecoplanar with a top surface 190 of porous dielectric layer 160.

FIGS. 4A through 4C are cross sectional views of a method of fabricatinga dual damascene wire according to another embodiment of the presentinvention. In FIG. 4A, conformal electrically conductive layer 165 isformed on all exposed surfaces of dielectric layer 140 and wires 105 andelectrically conductive layer 170 of sufficient thickness to overfilltrenches 150A (see FIG. 3A) is formed on top of conductive layer 165.

In FIG. 4B, a CMP is performed to form damascene wires 175 havingintegral vias 180, the vias being in physical and electrical contactwith wires 105. Top surfaces 185 of wires 175 are coplanar with a topsurface 145A of dielectric layer 140.

In FIG. 4C, dielectric layer 140 (see FIG. 4B) is heated to atemperature high enough to fully cure the dielectric layer creating aporous dielectric layer 160 having pores 162.

EXAMPLES

The poly-oxycarbosilane polymer was purchased from Starfire, Inc.Silanol containing materials are methylsilsesquioxane polymers obtainedfrom JSR Micro Corp. The thermal acid generator was purchased from CIBAor Aldrich Chemical Company. All the other chemicals were purchased fromAldrich Chemical Company. The following examples are intended to providethose of ordinary skill in the art with a complete disclosure anddescription of how to prepare and use the compositions disclosed andclaimed herein. Efforts have been made to ensure accuracy with respectto numbers (e.g., amounts, temperature, etc.), but allowance should bemade for the possibility of inadvertent errors and deviations.

The imprints of the imprinting formulations were fabricated on Instron5500R tool. The imprint force applied was set to approximately 400newtons. Films thicknesses and refractive indices were measured using aFilmetrics F20 Thin-Film Measurement System. Dielectric constants weredetermined using a capacitance bridge with an HP 4192A impedanceanalyzer using a metal insulator semi-conductor structure. Measurementswere done at 25° C. and 100 KHz. Young's modulus measurements wereobtained using a Fraunhofer LAWave surface acoustic wave spectrometer(SAWS) operating between 50 MHz-200 MHz and sampling each specimen atfive different spots. Densities were determined by specular x-rayreflectivity.

Example 1 Synthesis of a Low-K Porous Film Based onDimethoxy-Polycarbosilane

A low-k composition was formulated with 2.24 g dimethoxy-polycarbosilane(20 Wt % in 1-methoxy-2-propanol), 0.56 g MSSQ (GR-650, or JSR low MW,or JSR high MW, 20 Wt % in 1-methoxy-2-propanol), 1.2 g porogen(heptakis(2,3,6-tri-O-methyl-beta cyclodextrin) or PPG 6 k, 20 wt % in1-methoxy-2-propanol) and 0.0448 g of TAG. This mixture is spin-coated@3 k for 30 sec on a silicon wafer. The film is cured at 120° C. for 1 hand then at 450° C. for 2 h (heating rate: 5 c/min). Results arepresented in Table 1.

TABLE 1 SYNTHESIS AND PROPERTIES OF POROUS POLY- OXYCARBOSILANE FILMSPorogen (loading Thickness E_(SAWS) MSSQ Wt %) (nm) RI k @ 25 C. (GPa)GR-650 PPG (30) 454.29 1.2742 2.17 1.37 GR-650 CD (30) 415.09 1.2872 N/A0.90 JSR (low MW) PPG (30) 432.58 1.2654 2.19 1.07 JSR (low MW) CD (30)356.51 1.2689 2.23 1.69 JSR (high MW) PPG (30) 543.49 1.2383 1.91 0.89JSR (high MW) CD (30) 360.70 1.3321 N/A 3.53

Evidence of cross-linking between the poly-oxycarbosilane and the MSSQwas obtained using FTIR. Indeed the IR spectrum of the porous films showthe band characteristic of Si—CH2-Si at 1350 cm-1 from thepoly-oxycarbosilane, as well as the band characteristic of Si—CH3 at1280 cm-1 from the MSSQ.

Solutions composed of the dimethoxy polycarbosilane and TAG or MSSQ werealso spin-coated and cured under identical conditions. No films wereobtained after the thermal process demonstrating that the threeaforementioned components are necessary to promote the cross-linking ofthe poly-oxycarbosilane polymer.

Example 2 Nanoimprinting of Low-K Composition Based onDimethoxy-Polycarbosilane

A solvent free low-k formulation for nanoimprinting was formulated asfollows: 0.168 g dimethoxy-polycarbosilane, 0.042 g GR-650 (flakes), and0.0168 g of TAG. This mixture is spin-coated @3 k for 30 sec on asilicon wafer after which a mold is placed over the film and compressedwith a force of 400N. The film is cured at 120° C. for 1 h and then themold is removed. After rinsing the film several times with acetone allthe features remained intact, thus indicating that cross-linking hadtaken place at this stage. In a second processing step this imprintedfilm was cured at 450° C. for two hours. A top down SEM of nominal 30micron line/space features obtained are illustrated in FIG. 5.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. Recitation of ranges of values herein are merely intended toserve as a shorthand method of referring individually to each separatevalue falling within the range, unless otherwise indicated herein, andeach separate value is incorporated into the specification as if it wereindividually recited herein. The use of any and all examples, orexemplary language (e.g., “such as”) provided herein, is intended merelyto better illuminate the invention and does not pose a limitation on thescope of the invention unless otherwise claimed. No language in thespecification should be construed as indicating any non-claimed elementas essential to the practice of the invention.

The description of the embodiments of the present invention is givenabove for the understanding of the present invention. It will beunderstood that the invention is not limited to the particularembodiments described herein, but is capable of various modifications,rearrangements and substitutions as will now become apparent to thoseskilled in the art without departing from the scope of the invention.Therefore, it is intended that the following claims cover all suchmodifications and changes as fall within the true spirit and scope ofthe invention.

1. A composition comprising a silanol, a reaction initiator, and apolymer comprising a repeating unit having a structure selected fromstructures I and II:

wherein each of R, R₁, R₂ and R₃ is independently selected from hydrido,C₁₋₆ alkyl and haloalkyl; C₄₋₇ cycloalkyl and halocycloalkyl; C₁₋₆alkenyl and haloalkenyl; C₃₋₄ alkylenylcarbonyloxy; C₅₋₁₀cycloalkylenylcarbonyloxy and C₆₋₁₂ aryl and haloaryl; x is 1-4 andn=2-5000.
 2. The composition of claim 1, where the silanol is selectedfrom the group consisting of organosilicate and R_(m)Si(OH)_(4-m),wherein each R_(m) is independently selected from hydrido, C₁₋₆ alkyland haloalkyl, C₁₋₆ alkenyl and haloalkenyl, C₂₋₁₂ aryl and haloaryl. 3.The composition of claim 2, where the organosilicate includessilsesquioxane.
 4. The composition of claim 3, wherein thesilsesquioxane has a formula selected from the group consisting ofR₃SiO_(1.5) and R₄SiO_(1.5)—SiO₂, wherein R₃ and R₄ are independentlyselected from C₁₋₆ alkyl and C₆₋₁₂ aryl.
 5. The composition of claim 1,where the reaction initiator is selected from the group consisting of aphoto radical initiator, a thermal radical initiator, a photoacidgenerator, a thermal acid generator, a photo base generator, and athermal base generator.
 6. The composition of claim 1, wherein thereaction initiator is a photo radical initiator selected from the groupconsisting of an acetophenone, anisoin, an anthraquionone, abenzophenone, a benzoin ether, and benzyl.
 7. The composition of claim1, wherein the reaction initiator is a photoacid generator.
 8. Thecomposition of claim 7, wherein the photoacid generator is selected fromthe group consisting of a sulfonium salt, an iodonium salt, benzointosylate, and materials represented by structures (III), (IV), and (V):


9. The composition of claim 1, wherein the reaction initiator is athermal acid generator.
 10. The composition of claim 9, wherein thethermal acid generator is selected from the group consisting of 2,4,4,6tetrabromocyclohexadienone, benzoin tosylate, and 2-nitrobenzyltosylate.
 11. The composition of claim 1, where the composition furtherincludes a pore generator.
 12. The composition of claim 9, wherein thepore generator is selected from the group consisting of a polyester, apolylactide, a polystyrene, a substituted polystyrene, a poly-alphamethyl styrene, a substituted poly-alpha methyl styrene, an aliphaticolefin, a polynorbornene, a polyacrylate, a polymethacrylate, and analiphatic polyether.
 13. A composition comprising a silsesquioxane, anacid generator, and a polymer comprising a repeating unit having astructure selected from structures I and II:

wherein each of R, R₁, R₂, and R₃ is independently selected from hydridoand C₁₋₆ alkyl and n=2-500.
 14. The composition of claim 13, wherein thesilsesquioxane has a formula selected from the group consisting ofR₃SiO_(1.5) and R₄SiO_(1.5)—SiO₂, wherein R₃ and R₄ are independentlyselected from C₁₋₆ alkyl and C₆₋₁₂ aryl.
 15. The composition of claim13, wherein the acid generator is selected from the group consisting ofa photoacid generator and a thermal acid generator.
 16. The compositionof claim 15, wherein the photoacid generator is selected from the groupconsisting of a sulfonium salt, an iodonium salt, benzoin tosylate, andmaterials represented by structures (III), (IV), and (V):


17. The composition of claim 15, wherein the thermal acid generator isselected from the group consisting of 2,4,4,6tetrabromocyclohexadienone, benzoin tosylate, and 2-nitrobenzyltosylate.
 18. The composition of claim 13, where the composition furtherincludes a pore generator.
 19. The composition of claim 18, wherein thepore generator is selected from the group consisting of a polyester, apolylactide, a polystyrene, a substituted polystyrene, a poly-alphamethyl styrene, a substituted poly-alpha methyl styrene, an aliphaticolefin, a polynorbornene, a polyacrylate, a polymethacrylate, and analiphatic polyether.